CN113802017A - Method for separating and recovering aluminum in acid leachate of waste lithium iron phosphate battery positive electrode material by extraction method - Google Patents

Method for separating and recovering aluminum in acid leachate of waste lithium iron phosphate battery positive electrode material by extraction method Download PDF

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CN113802017A
CN113802017A CN202111076182.7A CN202111076182A CN113802017A CN 113802017 A CN113802017 A CN 113802017A CN 202111076182 A CN202111076182 A CN 202111076182A CN 113802017 A CN113802017 A CN 113802017A
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extraction
acid
aluminum
iron phosphate
solution
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周康根
彭佳乐
吴业惠子
高峰
胡舜聪
陈伟
赖复兴
张雪凯
文剑
彭长宏
陈伟军
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Guangdong Zhongjin Lingnan Environmental Protection Engineering Co ltd
Hunan Nonfemet & Komeng Environmental Protection Technology Co ltd
Central South University
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Guangdong Zhongjin Lingnan Environmental Protection Engineering Co ltd
Hunan Nonfemet & Komeng Environmental Protection Technology Co ltd
Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

本发明公开了一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，该方法是废旧磷酸铁锂电池正极材料酸性浸出液采用含有长链烷基膦酸萃取剂的有机相进行萃取三价铝离子，萃取有机相经过硫酸‑硫酸钾混合溶液进行反萃取，得到硫酸铝钾溶液，萃余液为含二价铁离子和锂离子的溶液。该方法充分利用溶液体系中Al3+的电荷数要高于Fe2+和Li+的特性，通过选择带有长链烷基的膦酸萃取剂对溶液体系中的Al3+进行选择性萃取分离，Fe2+和Li+留在浸出液中，奠定了再合成磷酸铁锂电池材料的基础，同时实现了溶液体系中Al3+的分离与再利用。The invention discloses a method for separating and recovering aluminum in the acid leaching solution of the positive electrode material of waste lithium iron phosphate battery by extraction method. Trivalent aluminum ions are extracted, and the extracted organic phase is back-extracted with a sulfuric acid-potassium sulfate mixed solution to obtain a potassium aluminum sulfate solution, and the raffinate is a solution containing ferrous ions and lithium ions. The method makes full use of the fact that the charge number of Al 3+ in the solution system is higher than that of Fe 2+ and Li + , and selects the phosphonic acid extractant with long-chain alkyl groups to selectively extract Al 3+ in the solution system. After separation, Fe 2+ and Li + remain in the leaching solution, which lays the foundation for the resynthesis of lithium iron phosphate battery materials, and at the same time realizes the separation and reuse of Al 3+ in the solution system.

Description

Method for separating and recovering aluminum in acid leachate of waste lithium iron phosphate battery positive electrode material by extraction method
Technical Field
The invention relates to a method for separating aluminum from acid leachate of a positive electrode material of a waste lithium iron phosphate battery, in particular to a method for separating aluminum from the acid leachate of the positive electrode material of the waste lithium iron phosphate battery by using an extraction method, and belongs to the technical field of waste lithium ion battery recovery and metallurgical environmental engineering.
Background
Lithium-ion batteries (LIBs) are widely used in the fields of new energy automobiles, information appliances, base station energy storage and the like due to their excellent characteristics of high energy density, high average output voltage, no memory effect, quick charging, wide temperature range and the like. Lithium ion batteries are mainly classified into Lithium cobalt oxide batteries, nickel-cobalt-manganese ternary batteries, and Lithium iron phosphate (LFP) batteries. Statistically, the production capacity of lithium ion batteries has increased from 56 hundred million in 2015 to 154 hundred million in 2019. The related statistics and model prediction results show that the output of the lithium ion battery in China can reach 283 hundred million in 2023. Among them, LFP batteries are increasingly valued by the market due to their significant advantages of high specific discharge capacity, stable discharge capacity, good cycle performance, strong thermal stability, no memory effect, low price, etc. However, the service cycle of the LFP battery is generally 5-8 years, and when the remaining capacity is 80%, the LFP battery needs to be retired, and when the remaining capacity is 60%, the LFP battery needs to be completely scrapped. The next two years are the retirement peak period of the lithium iron phosphate power battery in the field of new energy automobiles which are put into the first wave of China. The ministry of industry and informatization of the people's republic of China clearly indicates that the recycling of waste power batteries of new energy automobiles in China is already on an initial scale, but the recycling of LFP batteries faces the problem of poor economy, and the vigorous development of the LFP batteries is restrained. Therefore, the realization of the full-component recycling of the waste LFP battery material in a green and economic way is a necessary requirement for realizing the sustainable development of the battery industry.
The LFP battery consists of a metal shell, an organic electrolyte, a diaphragm and positive and negative electrode materials. The aluminum foil is connected with the positive electrode of the battery, and the copper foil is connected with the negative electrode of the battery. The wet process is a mainstream technology for recycling waste LFP battery materials at present, and the process is based on discharging, disassembling and sorting the waste LFP batteries, leaching part or all of valuable metals in an LFP positive electrode material by using various inorganic acids or organic acids, and then realizing the recycling of the lithium iron phosphate battery through subsequent separation and synthesis. The existing process for selectively recovering lithium is quite mature, but the current-stage technology cannot realize the complete separation of a current collector aluminum foil and an LFP positive electrode material in the separation process. Moreover, because the olivine-structured lithium iron phosphate is very stable, the reaction of the active metal aluminum and the acid is faster than the leaching process of the lithium iron phosphate powder. Therefore, aluminum is completely dissolved in the process of acid leaching the LFP positive electrode material, so that the aluminum enters a lithium iron phosphate precursor-hydrated iron phosphate product synthesized by using the acid leaching solution, the introduction of the aluminum can obviously reduce the battery capacity of the regenerated LFP battery, the electrochemical performance of the battery is influenced, and iron and phosphorus in the waste materials are difficult to be effectively utilized in a high-value mode. Therefore, in the process of recycling valuable metals in the acid leachate of the waste LFP battery positive electrode material, aluminum in the acid leachate needs to be preferentially separated.
At present, few reports about the purification and aluminum removal of acid leaching solution of waste lithium iron phosphate battery materials at home and abroad are reported. Chinese patent (publication No. CN 106910889B) discloses a method for regenerating positive active substances from waste lithium iron phosphate batteries, which is realized by adopting a combined process of sulfuric acid leaching-iron powder reduction-alkali liquor aluminum precipitation-phosphorus source supplement-lithium iron phosphate regeneration on the basis of salt water discharge and disassembly, and the method mainly comprises the step of adjusting the pH value of a solution system by adding active metal hydroxide to ensure that Al is regenerated3+With Al (OH)3The form of (a) precipitates. The traditional chemical precipitation method has undesirable treatment effect, and white Fe is generated due to overhigh local pH caused by adding hydroxide3(PO4)2And other active metal ions entering the solution system easily enter the regenerated lithium iron phosphate battery material, so that the electrochemical performance of the lithium iron phosphate battery material is reduced. Chinese patent (publication No. CN 110643814A) discloses a method for removing aluminum and recovering waste lithium iron phosphate batteries, which is based on iron powder reduction and also adds a pH regulator: the pH value of the aluminum-containing acidic solution is adjusted by the synergy of urea, hexamethylenetetramine and ammonium dihydrogen phosphate, and Al in the solution system is adjusted3+Removed as phosphate precipitate. Although the method has good effect, other impurity ions are introduced in the process of adjusting the pH, and the method greatly loses the phosphorus source. In addition, excessive iron powder is also likely to enter the regenerated battery, affecting the relevant performance. In addition, the valuable metal aluminum finally enters waste residues which are easy to cause secondary pollution, and is not effectively recycled.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a long-chain alkyl phosphonic acid-based extractant for extracting different cations in acid leaching solution of lithium iron phosphate battery positive electrode materialThe difference of the charges selectively extracts Al in the acid leaching solution of the anode material of the waste lithium iron phosphate battery3+The method of (1). The method makes full use of Al in a solution system3+Has a charge number higher than that of Fe2+And Li+By selecting a phosphonic acid extractant with a long chain alkyl group for Al in the solution system3+By selective extraction separation of Fe2+And Li+Remains in the leaching solution, lays a foundation for re-synthesizing the lithium iron phosphate battery material, and simultaneously realizes Al in a solution system3+Separation and reuse of (1).
In order to achieve the technical purpose, the invention provides a method for separating and recovering aluminum in acid leachate of a waste lithium iron phosphate battery positive electrode material by an extraction method.
The key point of the technical scheme of the invention is that Al in the acidic leaching solution of the anode material of the waste lithium iron phosphate battery is fully utilized3+With Fe2+And Li+The difference of charges between the two extracts causes different affinities with the long-chain alkyl phosphonic acid extractant, so that the long-chain alkyl phosphonic acid extractant is used for selectively extracting and separating Al in the solution system3+The method realizes the separation of aluminum ions from other valuable metal ions in an acidic leaching solution system, further achieves the purpose of separating and recycling the aluminum ions, thoroughly removes the aluminum ions in the dealuminized raffinate, is rich in ferrous ions and lithium ions, can be further used for preparing battery-grade iron phosphate and lithium carbonate, and can be used for synthesizing a lithium iron phosphate battery material with good electrochemical performance through carbothermic reduction, thereby realizing the cyclic regeneration of waste materials. The organic phase rich in aluminum ions can be subjected to back extraction by using a sulfuric acid + potassium sulfate solution and effectively enriched to obtain a product of aluminum potassium sulfate, and the regenerated organic phase can be reused. The method has the advantages of strong selectivity, high aluminum removal rate, reusability, low cost, no secondary pollution and the like, and satisfies the requirement of' two pairsThe construction requirement of the type society.
As a preferable scheme, the concentration of trivalent aluminum ions in the acid leaching solution of the waste lithium iron phosphate battery positive electrode material is 0.5-12.8 g/L, the concentration of divalent iron ions is 20.1-90.8 g/L, and the concentration of lithium ions is 3.1-15.7 g/L.
As a preferable scheme, the long-chain alkyl phosphonic acid extractant at least contains 1-2C6～C16A long chain alkyl group. More preferably, the organic phosphonic acid long-chain alkyl acidic extractant is used for Al in the acid leaching solution of the waste lithium iron phosphate waste rich in trivalent aluminum ions, lithium ions and divalent iron ions3+The selective extraction capability is stronger, and the aluminum and other metal ions in the solution system are easy to separate. And other types of long-chain alkyl acid extractants, such as organic carboxylic acids (such as mixed fatty acids, naphthenic acids, versatic acids and the like), organic sulfonic acids (such as 5, 8-dinonyl-2-naphthalenesulfonic acid and the like) or phosphinic acids (such as di (2,4, 4-trimethylpentyl) phosphonic acid and the like), have poor selectivity on aluminum ions in a coexisting solution system of lithium ions, ferrous ions and aluminum ions, and are difficult to separate efficiently. As a further preferred embodiment, the long-chain alkyl phosphonic acid extractant is selected from at least one of mono (2-ethylhexyl) phosphonic acid, mono-dodecylphosphonic acid, di (2-ethylhexyl) phosphonic acid, di (1-methylhexyl) phosphonic acid.
As a preferred embodiment, the long-chain alkyl phosphonic acid extractant is subjected to saponification pretreatment. The long-chain alkyl phosphonic acid extractant is substantially organic acid and can continuously release H in the extraction process+Thereby reducing the pH of the solution system and affecting the extraction performance. In order to ensure continuous and stable operation of the extraction process, the extractant is saponified prior to the extraction process. Currently used saponifiers include: one or more of concentrated ammonia water, potassium hydroxide or sodium hydroxide and other optional alkali. In order to introduce other impurity cations as little as possible and reduce the influence on the synthesis of subsequent battery materials, the preferable saponifier is selected to be strong ammonia water.
As a preferred embodiment, the organic phase containing the long-chain alkyl phosphonic acid extractant comprises the following components in percentage by volume: 5-80% of a long-chain alkyl phosphonic acid extractant; 10-90% of diluent (such as sulfonated kerosene, 200 solvent oil, octane and the like); 0-50% of liquid water-insoluble alcohol and/or phenol polar modifier (ethanol, higher alcohol, neutral phosphorus extractant TBP and the like). The total volume of the organic phase is 100%, and the preferable volume percentage of the long-chain alkyl phosphonic acid extractant in the organic phase is 20-50%; the preferable volume percentage of the diluent is 50-80%, and the specific preferable volume percentage of the modifier is 0-20%. The extraction process has rapid phase separation, and no modifier is added to improve the phase separation condition.
As a preferred embodiment, the diluent comprises at least one of kerosene, toluene, chloroform, carbon tetrachloride and heptane. The common diluents weaken the action of the extractant with metal ions by forming hydrogen bonds with the extraction functional group-OH or P ═ O, and are sparingly soluble or insoluble in water. Further preferred is kerosene, added to facilitate the phase separation and extraction reactions.
As a preferred embodiment, the extraction conditions are: the volume ratio of the organic phase to the water phase is 0.1-8: 1, the extraction pH is 0.1-3.4, the extraction temperature is 8-70 ℃, the extraction time is 2-60 min, and the phase separation time is 1-30 min. The volume ratio of the organic phase to the aqueous phase is preferably 0.5 to 2: 1. The preferable pH value is 0.5-2.7; the extraction temperature is 8-70 ℃, the extraction time is 2-60 min, and the phase separation time is 1-30 min. The volume ratio of the organic phase to the water phase is preferably 0.5-2: 1, the extraction temperature is preferably 20-60 ℃, the extraction time is preferably 8-20 min, and the phase separation time is preferably 2-5 min.
In a preferred embodiment, the back extraction uses a mixed solution of dilute acid and potassium sulfate as a back extractant. The stripping agent is dilute sulfuric acid solution. The concentration of the dilute sulfuric acid is 0.05-5.8 mol.L-1More preferably 1 to 5.2 mol.L-1. The concentration of the potassium sulfate is 0.01-3 mol.L-1More preferably 0.5 to 2.5 mol.L-1。
As a preferred embodiment, the stripping conditions are: the volume ratio of the organic phase to the water phase is 0.1-8: 1, the back extraction temperature is 20-60 ℃, the back extraction time is 2-60 min, and the phase separation time is 1-20 min. The volume ratio of the organic phase/the aqueous phase is preferably 0.5 to 2: 1. The preferable back extraction temperature is 20-50 ℃. The preferable extraction time is 8-20 min. The preferable phase separation time is 2-5 min.
As a preferable scheme, the pH value of the acidic leaching solution of the anode material of the waste lithium iron phosphate battery is adjusted to be 1.5-4.
The invention relates to an acidic leachate of a positive electrode material of a waste lithium iron phosphate battery, which is obtained by discharging and disassembling the waste lithium iron phosphate battery by a conventional method to obtain the positive electrode material (usually containing a small amount of aluminum foil), and leaching the positive electrode material by one or more of common acids such as sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, acetic acid and the like to obtain the acidic leachate containing aluminum, lithium and iron.
After the back extraction, the organic phase enters a saponification regeneration stage. The preferred saponification regenerant in this process is concentrated ammonia.
The lithium iron phosphate anode powder (containing a small amount of aluminum foil) mainly undergoes the following chemical reactions in the leaching process:
2LiFePO4+6H+＝2Li++2Fe2++2H3PO4；
FePO4+3H+＝Fe3++H3PO4；
2Al+6H+＝2Al3++3H2；
Al2O3+6H+＝2Al3++3H2O。
the raffinate is used for preparing lithium iron phosphate: supplementing an excessive phosphorus source in the raffinate, adding excessive hydrogen peroxide for oxidation reaction, adjusting the pH of the aluminum-removed liquid to be 0.4-3.9, performing precipitation reaction at the temperature of 70-120 ℃, and performing solid-liquid separation to obtain ferric phosphate dihydrate precipitate and a lithium-rich solution; heating, dehydrating and calcining the ferric phosphate dihydrate precipitate to obtain ferric phosphate; adding sodium carbonate into the lithium-rich solution for precipitation, carrying out solid-liquid separation to obtain lithium carbonate, and drying and calcining; and adding glucose into the lithium carbonate and the iron phosphate for carbothermic reduction to obtain the lithium iron phosphate. The phosphorus source of the invention is mainly phosphate radical-containing substances, such as phosphoric acid, ammonium dihydrogen phosphate and ammonium monohydrogen phosphate. Hydrogen peroxide primarily oxidizes ferrous iron to ferric iron, a process well known in the art.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) according to the invention, through an acid leaching-extraction separation technology, aluminum ions in the acid leaching solution of the waste lithium iron phosphate anode material can be effectively separated, the removal rate of the aluminum ions can reach more than 99%, and iron, lithium and phosphorus in a solution system are not substantially lost, so that effective separation of aluminum and other valuable metals is realized, and a foundation is laid for subsequent recycling of iron, lithium and phosphorus;
2) according to the invention, the concentration of aluminum ions can be effectively enriched to 32g/L through extraction and back extraction, so that the problem that aluminum is difficult to separate in the wet recovery process of the waste lithium iron phosphate anode material is solved, and the reutilization is realized;
3) according to the invention, after the aluminum ions are extracted and separated, the aluminum ions are thoroughly removed, the raffinate can be used for preparing battery-grade iron phosphate and lithium carbonate, and the lithium iron phosphate battery material with good electrochemical performance can be synthesized again through a subsequent process, so that the strategic requirements of sustainable development are met;
4) the invention has simple process, low equipment investment, repeated use and environmental protection.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
The acid leaching solutions of the positive electrode materials of the waste lithium iron phosphate batteries in the following examples and comparative examples are based on positive and negative electrode powders obtained by discharging, disassembling and sorting the waste lithium iron phosphate batteries by a conventional method, and the solution obtained by acid leaching is utilized, and the concentration of dilute sulfuric acid is controlled to be 3.8 mol.L-1The liquid-solid ratio is 4ml g-1Leaching at 25 deg.c, magnetically stirring for 3 hr, and solid-liquid separating to obtain acid leaching liquid.
Example 1
Taking the acid leaching solution of the anode material of the waste lithium iron phosphate battery with the aluminum content of 4.9g/L, the iron content of 87.2g/L and the lithium content of 10.9g/L, adjusting the pH to 1.72, taking 30% of di (1-methyl hexyl) phosphonic acid and 70% of kerosene obtained after saponification of concentrated ammonia water as an extraction system, extracting under the condition that the volume ratio of an organic phase to a water phase is 1:1, wherein the extraction time is 15min, the extraction temperature is 30 ℃, carrying out phase separation for 2 min after the reaction is finished, taking the water phase to send ICP for analyzing the concentrations of aluminum, iron and lithium in raffinate, and the concentration of Al in the raffinate is 186.2ppm, so that the single-stage extraction rate of aluminum is 96.2%, the loss rate of iron is 1.7% and the loss rate of lithium is 0.5%.
In the embodiment, 3.8mol/L dilute sulfuric acid +0.9mol/L potassium sulfate is used as a stripping agent, the volume ratio of the loaded organic phase to the stripping agent is 1:1, the mixture is oscillated for 15min at 25 ℃, the phase separation is carried out for 3 min after the reaction is finished, the water phase is taken and sent to ICP (inductively coupled plasma) to analyze the concentration of aluminum in the stripping solution, and the single-stage stripping rate is 72.6 percent.
Example 2
Taking the acid leaching solution of the anode material of the waste lithium iron phosphate battery with the aluminum content of 2.9g/L, the iron content of 89.2g/L and the lithium content of 11.2g/L, adjusting the pH to 2.32, taking 30% of monododecyl phosphonic acid and 70% of kerosene obtained after saponification of concentrated ammonia water as an extraction system, extracting under the condition that the volume ratio of an organic phase to a water phase is 1:4, the extraction time is 10min, the extraction temperature is 25 ℃, carrying out phase separation for 2 min after the reaction is finished, taking the water phase to carry out ICP analysis on the concentrations of aluminum, iron and lithium in raffinate, wherein the concentration of Al in the raffinate is 919.3ppm, the single-stage extraction rate of aluminum is 68.3%, the loss rate of iron is 1.2% and the loss rate of lithium is 0.5%.
In the embodiment, 4.8mol/L dilute sulfuric acid +1.0mol/L potassium sulfate is used as a stripping agent, the volume ratio of the loaded organic phase to the stripping agent is 1:1, the mixture is oscillated for 15min at 25 ℃, the phase separation is carried out for 3 min after the reaction is finished, and the water phase is taken and sent to ICP (inductively coupled plasma) to analyze the concentration of aluminum in the stripping solution, so that the single-stage stripping rate is 89.6%.
Example 3
Taking the acid leaching solution of the anode material of the waste lithium iron phosphate battery with the aluminum content of 2.7g/L, the iron content of 90.4g/L and the lithium content of 11.4g/L, adjusting the pH to 2.32, taking 20 percent of mono (2-ethylhexyl) phosphonic acid and 80 percent of kerosene after the saponification of concentrated ammonia water as an extraction system, extracting under the condition that the volume ratio of an organic phase to a water phase is 1:1, the extraction time is 10min, the extraction temperature is 25 ℃, carrying out phase separation for 2 minutes after the reaction is finished, taking the water phase to send ICP for analyzing the concentrations of aluminum, iron and lithium in raffinate, wherein the concentration of Al in the raffinate is 580.5ppm, the single-stage extraction rate of the aluminum is 78.5 percent, the loss rate of the iron is 1.1 percent and the loss rate of the lithium is 0.6 percent.
In the embodiment, 4.8mol/L dilute sulfuric acid +1.0mol/L potassium sulfate is used as a stripping agent, the volume ratio of the loaded organic phase to the stripping agent is 1:1, the mixture is oscillated for 15min at 25 ℃, the phase separation is carried out for 3 min after the reaction is finished, the water phase is taken and sent to ICP (inductively coupled plasma) to analyze the concentration of aluminum in the stripping solution, and the single-stage stripping rate is 90.2%.
Example 4
Taking the acid leaching solution of the anode material of the waste lithium iron phosphate battery with the aluminum content of 2.7g/L, the iron content of 90.4g/L and the lithium content of 11.4g/L, adjusting the pH to 2.32, taking 40% of di (2-ethylhexyl) phosphonic acid and 60% of kerosene obtained after saponification of concentrated ammonia water as an extraction system, extracting under the condition that the volume ratio of an organic phase to a water phase is 1:1, wherein the extraction time is 10min, the extraction temperature is 25 ℃, carrying out phase separation for 2 min after the reaction is finished, taking the water phase to send ICP for analyzing the concentrations of aluminum, iron and lithium in raffinate, and the concentration of Al in raffinate is 2.7ppm, so that the single-stage extraction rate of aluminum is 99.9%, the loss rate of iron is 1.1%, and the loss rate of lithium is 0.6%.
In the embodiment, 5.2mol/L dilute sulfuric acid +1.0mol/L potassium sulfate is used as a stripping agent, the volume ratio of the loaded organic phase to the stripping agent is 1:1, the mixture is oscillated for 10min at 25 ℃, the phase separation is carried out for 3 min after the reaction is finished, the water phase is taken and sent to ICP (inductively coupled plasma) to analyze the concentration of aluminum in the stripping solution, and the single-stage stripping rate is 91.3 percent.
Example 5
Taking the acid leaching solution of the anode material of the waste lithium iron phosphate battery with the aluminum content of 3.1g/L, the iron content of 88.4g/L and the lithium content of 11.1g/L, adjusting the pH to 3.42, taking 30 percent of di (2-ethylhexyl) phosphonic acid and 70 percent of kerosene obtained after saponification of concentrated ammonia water as an extraction system, extracting under the condition that the volume ratio of an organic phase to a water phase is 1:1, wherein the extraction time is 10min, the extraction temperature is 25 ℃, carrying out phase separation for 2 minutes after the reaction is finished, taking the water phase to send ICP for analyzing the concentrations of aluminum, iron and lithium in raffinate, and the concentration of Al in the raffinate is 6.2ppm, so that the single-stage extraction rate of aluminum is 99.8 percent, the loss rate of iron is 7.8 percent and the loss rate of lithium is 0.6 percent.
In the embodiment, 3.8mol/L dilute sulfuric acid +1.0mol/L potassium sulfate is used as a stripping agent, the volume ratio of the loaded organic phase to the stripping agent is 1:1, the mixture is oscillated for 10min at 25 ℃, the phase separation is carried out for 3 min after the reaction is finished, the water phase is taken and sent to ICP (inductively coupled plasma) to analyze the concentration of aluminum in the stripping solution, and the single-stage stripping rate is 88.3 percent.
Comparative example 1
Taking the acid leaching solution of the anode material of the waste lithium iron phosphate battery with the aluminum content of 4.9g/L, the iron content of 87.2g/L and the lithium content of 10.9g/L, adjusting the pH to 1.72, taking unsaponifiable 30 percent di (1-methylhexyl) phosphonic acid and 70 percent kerosene as an extraction system, extracting under the condition that the volume ratio of an organic phase to a water phase is 1:1, the extraction time is 15min, the extraction temperature is 30 ℃, carrying out phase separation for 2 min after the reaction is finished, taking the water phase to send ICP to analyze the concentrations of aluminum, iron and lithium in raffinate, wherein the concentration of Al in the raffinate is 1656ppm, the single-stage extraction rate of aluminum is 66.2 percent, the loss rate of iron is 1.8 percent and the loss rate of lithium is 0.6 percent.
In the embodiment, 1.2mol/L dilute sulfuric acid is used as a stripping agent, the volume ratio of the loaded organic phase to the stripping agent is 1:1, the mixture is oscillated for 15min at 25 ℃, the phase separation is carried out for 3 min after the reaction is finished, and the water phase is taken and sent to ICP (inductively coupled plasma) to analyze the concentration of aluminum in the stripping solution, so that the single-stage stripping rate is 21.2%.
Comparative example 2
Taking the acid leaching solution of the anode material of the waste lithium iron phosphate battery with the aluminum content of 2.7g/L, the iron content of 90.4g/L and the lithium content of 11.4g/L, adjusting the pH to 2.42, taking 30% naphthenic acid and 70% kerosene obtained after saponification of concentrated ammonia water as an extraction system, extracting under the condition that the volume ratio of an organic phase to a water phase is 1:1, the extraction time is 10min, the extraction temperature is 25 ℃, carrying out phase separation for 2 minutes after the reaction is finished, taking the water phase to send ICP to analyze the concentrations of aluminum, iron and lithium in raffinate, wherein the concentration of Al in the raffinate is 2662ppm, the single-stage extraction rate of the obtained aluminum is 1.4%, the loss rate of the iron is 0.8% and the loss rate of the lithium is 0.1%.
In the embodiment, 4.8mol/L dilute sulfuric acid is used as a stripping agent, the volume ratio of the loaded organic phase to the stripping agent is 1:1, the mixture is oscillated for 10min at 25 ℃, the phase separation is carried out for 3 min after the reaction is finished, and the water phase is taken and sent to ICP (inductively coupled plasma) to analyze the concentration of aluminum in the stripping solution, so that the single-stage stripping rate is 48.3%.
The two comparative examples illustrate that even if an acidic extractant is used but a phosphonic acid extractant is not used, even if the phosphonic acid extractant is not saponified, the pH in the extraction process cannot be well controlled, so that selective extraction and separation of aluminum in an acid leaching solution cannot be realized, a good separation effect of an aluminum and a lithium iron solution cannot be obtained, and thus high-valued utilization of waste lithium iron phosphate battery materials cannot be effectively realized. In the back extraction process, the mixed solution of sulfuric acid and potassium sulfate is adopted to effectively promote the back extraction reaction, and the back extraction solution can be well recycled and is also beneficial to the recycling of the extractant.

Claims (10)

1.一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：废旧磷酸铁锂电池正极材料酸性浸出液采用含有长链烷基膦酸萃取剂的有机相进行萃取三价铝离子，萃取有机相经过硫酸-硫酸钾混合溶液进行反萃取，得到硫酸铝钾溶液，萃余液为含二价铁离子和锂离子的溶液。1. an extraction method separates and reclaims the method for aluminum in waste and old lithium iron phosphate battery positive electrode material acid leachate, it is characterized in that: waste and old iron phosphate battery positive electrode material acid leaching solution adopts the organic phase that contains long-chain alkyl phosphonic acid extractant to extract Trivalent aluminum ions are extracted, and the organic phase is extracted through sulfuric acid-potassium sulfate mixed solution for back extraction to obtain aluminum potassium sulfate solution, and the raffinate is a solution containing divalent iron ions and lithium ions. 2.根据权利要求1所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述废旧磷酸铁锂电池正极材料酸性浸出液中三价铝离子的浓度为0.5～12.8g/L，二价铁离子的浓度为20.1～90.8g/L，锂离子的浓度为3.1～15.7g/L。2. a kind of extraction method according to claim 1 separates and reclaims the method for aluminum in the acid leachate of waste and old lithium iron phosphate battery positive electrode material, it is characterized in that: in the acid leaching solution of described waste and old lithium iron phosphate battery positive electrode material, trivalent aluminum ion The concentration is 0.5-12.8 g/L, the concentration of divalent iron ion is 20.1-90.8 g/L, and the concentration of lithium ion is 3.1-15.7 g/L. 3.根据权利要求1所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述长链烷基膦酸萃取剂含有1～2个C6～C16长链烷基。3. a kind of extraction method according to claim 1, is characterized in that: the described long-chain alkyl phosphonic acid extractant contains 1～2 C 6 ~C 16 long chain alkyl. 4.根据权利要求3所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述长链烷基膦酸萃取剂选自单(2-乙基己基)膦酸、单十二烷基膦酸、二(2-乙基己基)膦酸、二(1-甲基己基)膦酸中至少一种。4. a kind of extraction method according to claim 3, is characterized in that: the described long-chain alkyl phosphonic acid extractant is selected from mono(2-ethyl) at least one of bis(2-ethylhexyl)phosphonic acid, monododecylphosphonic acid, bis(2-ethylhexyl)phosphonic acid, and bis(1-methylhexyl)phosphonic acid. 5.根据权利要求1、3或4所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述长链烷基膦酸萃取剂经过皂化预处理。5. a kind of extraction method according to claim 1,3 or 4 described the method for separating and reclaiming aluminium in the acid leachate of waste and old lithium iron phosphate battery positive electrode material, it is characterized in that: described long-chain alkylphosphonic acid extractant is pre-saponified through saponification. deal with. 6.根据权利要求1所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述含有长链烷基膦酸萃取剂的有机相包括以下体积百分比组分：长链烷基膦酸萃取剂5～80％；稀释剂10％～90％；液态非水溶性醇类和/或酚类极性改质剂0～50％。6. a kind of extraction method according to claim 1, is characterized in that: the described organic phase that contains long-chain alkylphosphonic acid extractant comprises following volume Percent components: 5-80% of long-chain alkylphosphonic acid extractant; 10-90% of diluent; 0-50% of liquid water-insoluble alcohol and/or phenolic polar modifier. 7.根据权利要求6所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述稀释剂包括煤油、甲苯、氯仿、四氯化碳和庚烷中至少一种。7. a kind of extraction method according to claim 6, is characterized in that: described thinner comprises kerosene, toluene, chloroform, carbon tetrachloride and heptyl at least one of alkanes. 8.根据权利要求1所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述萃取的条件为：有机相/水相体积比为0.1～8:1，萃取pH为0.1～3.4，萃取温度为8～70℃，萃取时间为2～60min，分相时间为1～30min。8. a kind of extraction method according to claim 1, is characterized in that: the condition of described extraction is: organic phase/aqueous phase volume ratio is 0.1～ 8:1, the extraction pH is 0.1 to 3.4, the extraction temperature is 8 to 70° C., the extraction time is 2 to 60 minutes, and the phase separation time is 1 to 30 minutes. 9.根据权利要求1所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述硫酸-硫酸钾混合溶液中硫酸的浓度为0.05～5.8mol·L-1，硫酸钾的浓度为0.01～3mol·L-1。9. a kind of extraction method according to claim 1, is characterized in that: the concentration of sulfuric acid in the described sulfuric acid-potassium sulfate mixed solution is 0.05～5.8mol ·L -1 , the concentration of potassium sulfate is 0.01 to 3 mol·L -1 . 10.根据权利要求1所述的一种萃取法分离回收废旧磷酸铁锂电池正极材料酸浸出液中铝的方法，其特征在于：所述反萃取的条件为：有机相/水相体积比为0.1～8:1，反萃取温度为20～60℃，反萃取时间为2～60min，分相时间为1～20min。10. a kind of extraction method according to claim 1, is characterized in that: the condition of described back-extraction is: organic phase/aqueous phase volume ratio is 0.1 ~8:1, the back extraction temperature is 20 to 60°C, the back extraction time is 2 to 60 minutes, and the phase separation time is 1 to 20 minutes.
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CN114657378A (en) * 2021-12-27 2022-06-24 昆明理工大学 A method for extraction, separation and recovery of valuable metals in the leaching solution of cathode materials of waste lithium batteries
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